US4794086A - Method for measurement of impurities in liquids - Google Patents

Method for measurement of impurities in liquids Download PDF

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US4794086A
US4794086A US06/801,305 US80130585A US4794086A US 4794086 A US4794086 A US 4794086A US 80130585 A US80130585 A US 80130585A US 4794086 A US4794086 A US 4794086A
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diameter
droplets
residue
liquid
particles
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Gerhard Kasper
Horng Y. Wen
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Liquid Air Corp
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Liquid Air Corp
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Assigned to LIQUID AIR CORPORATION ONE EMBARCADERO CENTER SAN FRANCISCO, CA 94111 A CA CORP reassignment LIQUID AIR CORPORATION ONE EMBARCADERO CENTER SAN FRANCISCO, CA 94111 A CA CORP ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KASPER, GERHARD, WEN, HORNG Y.
Priority to JP62500195A priority patent/JPH06105249B2/ja
Priority to EP87900412A priority patent/EP0247180A1/fr
Priority to PCT/US1986/002530 priority patent/WO1987003371A1/fr
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/06—Investigating concentration of particle suspensions
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/02—Investigating particle size or size distribution
    • G01N15/0205—Investigating particle size or size distribution by optical means
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/06—Investigating concentration of particle suspensions
    • G01N15/065—Investigating concentration of particle suspensions using condensation nuclei counters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/85—Investigating moving fluids or granular solids
    • G01N2021/8557—Special shaping of flow, e.g. using a by-pass line, jet flow, curtain flow
    • G01N2021/8564—Sample as drops
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
    • Y10T436/25875—Gaseous sample or with change of physical state

Definitions

  • This invention relates to the measurement of impurities in liquids as, for example, between 0.01 ppm to 10 4 ppm, and especially to a method for the rapid measurement of impurities in ultrapure liquids containing sub-ppm concentrations of impurities.
  • the standard test method used to detect impurities in liquids measures the residue remaining after evaporation of a volatile liquid and heating of the dish and residue at 105° C. for 30 minutes.
  • the Residue after Evaporation test method is laid down in the BOOK OF SEMI STANDARDS 1985, Volume 1, Chemicals Divisions, p. 6, section 3.3, Determination of Residue After Evaporation; in the Annual Book of ASTM Standards, 1984, Designation: D 1353-83, Standard Test Method for Nonvolatile Matter in Volatile Solvents for use in Paint, Varnish, Lacquer, and related products; as well as in Analytical Chemistry, Volume 50 No. 7, June 1978 issue, in the article entitled "Analysis of High Purity Chemicals: Examination and Improvement of the Residue After Evaporation Test for Solvents", by Campbell and Hallquist.
  • the test methods are basically the same.
  • the last method includes cutting a circle of "household type" aluminum foil having a thickness of 0.006 cm and about 20 cm in diameter. After washing with the liquid to be measured for impurities and air drying, the foil is pressed around the bottom of an 800 ml beaker. The resulting aluminum foil dish is then heated at 105° C. for thirty minutes. In cases where the liquid used attacks aluminum, a platinum dish is used. The dish is then cooled in a desiccator charged with calcium chloride for about 30 to 45 minutes.
  • Static electricity is then discharged with a radioactive source and the dish is then weighed.
  • the dish is placed into a Thiers assembly having nitrogen flowing into it which has been filtered through a 0.8 um membrane filter.
  • An amount of the liquid to be measured which is equivalent to 200 grams is added to the dish.
  • the dish and liquid are then exposed to a heat lamp placed above it and to a low temperature hot plate below. The heating is adjusted so that evaporation takes place at not more than 8 ml/min.
  • the dish still in the Thiers assembly is placed in an oven at 105° C. for 30 minutes, followed by cooling in the same desiccator mentioned above. After about 35 to 45 minutes the static electricity is discharged and the resulting dish is then weighed. The weight of the residue can be determined by subtracting the original weight of the dish alone.
  • the accuracy of the above described method permits the detection of residues as low as 0.4 ppm. Possibility of error can originate from atmospheric contamination, contamination from the apparatus, loss of residue if transferred, cooling time of the dish before weighing, moisture pick-up from the air, and loss of residue through entrainment in escaping vapor.
  • the present invention addresses the needs of the semiconductor industry, as well as other industries requiring the rapid analysis of liquids for impurities contained therein.
  • the method is extremely accurate, faster, and more economical with regard to the small amount of liquid required than the standard method.
  • the basic requirements are that the liquid to be analyzed must be capable of being dispersed into droplets, be capable of evaporation, and be of a nature which can be contained in an appropriate vessel without reacting or dissolving its walls to add additional impurities.
  • the method of the invention includes dispersing the liquid to be measured for impurities into uniform droplets of a precisely known diameter D in a gas stream under ambient conditions.
  • the droplets are then evaporated rapidly to leave a residue particle having an unknown diameter d. Any static charge on the droplets and/or residue particles is then neutralized and the diameter d of the residue particles is then measured.
  • the residue concentration by volume, C v within the liquid can then be calculated according to the equation:
  • the liquid to be dispersed is dispersed preferably by means of a vibrating orifice generator wherein a liquid jet fed by a syringe pump is broken up in a controlled manner into highly uniform droplets by means of a piezoelectric vibrator.
  • the vibrator vibrates at a selectable frequency which controls the uniform size of the droplets.
  • a turbulent gas flow such as air or nitrogen to disperse the droplets and rapidly dry them, each droplet leaving behind the residue particle.
  • Neutralization of any static charge can be effected by use of a Krypton-85 radioactive neutralizer.
  • the gas stream of residue particles can be periodically passed through a heated zone to cause evaporation of organic impurities. This permits a determination of whether the residue particle is organic or inorganic. By comparing the size of the particle prior to exposure to heat with that of the size of the particle after exposure to heat, the amount of organic impurities can be determined.
  • the residue particles issuing from the droplet generator each have a diameter d which is measured according to the invention method.
  • any particle sizing device such as a light scattering spectrometer.
  • Other devices which can be used are described in the detailed description of the invention which follows.
  • FIG. 1 shows a schematic flow diagram of the method of the invention utilizing a particle source from a droplet generator and a laser light scattering particle spectrometer;
  • FIG. 2 shows a general schematic diagram of a light scattering particle spectrometer
  • FIG. 3 shows a schematic diagram of the process of the invention with emphasis on the droplet generator
  • FIG. 4 shows a schematic flow diagram of the invention process using an electrostatic classifier and a condensation nuclei counter
  • FIG. 5 shows a schematic diagram of an aerodynamic particle sizer.
  • FIG. 5 shows a schematic diagram of an aerodynamic particle sizer.
  • the accuracy of the invention method is dependent on accurate knowledge of the diameter D of a droplet of a liquid to be analyzed for impurities, and the measurement of the diameter d of the residue particle remaining after evaporation of the liquid from the droplet.
  • a vibrating orifice droplet generator is preferred for monodispersing uniform droplets into a gas stream.
  • a preferred droplet generator is Model 3450 availabe from TSI, Inc. This device is known in the scientific literature. See for example, Berglund, R. N. and Liu, B. Y. H. (1973) Eviron. Sci. Technol. 7, 147.
  • FIG. 3 A schematic of a droplet generator can be seen in FIG. 3.
  • a syrine pump 60 feeds liquid to be sampled at a preset flow rate into a chamber 62 where a vibrating orifice 64 produces identical, uniform droplets 66 one by one as the stream passes through the vibrating orifice.
  • the vibrating orifice 64 generates uniform droplets 66 by controlling the breakup of the liquid jet.
  • the production of non-uniform droplets is avoided by applying a periodic disturbance of an appropriate frequency in a regulated manner. This process produces highly uniform droplets having a standard deviation typically less than 1% of the median droplet size.
  • the vibrating orifice 64 is extremely small in size and the liquid solution from the syringe pump 60 is fed at a predetermined rate.
  • a piezoelectric ceramic vibrates the orifice 64 at a constant frequency, which vibration is driven by an oscillating voltage potential.
  • the turbulent air jet 68 acts to disperse the droplet and prevent coagulation.
  • a larger volume of filtered, clean, dry air is also added to the chamber 62 to induce evaporation of the liquid.
  • the droplets 66 pass upwardly through the chamber 62, they are exposed to the deionizing effects of a Krypton-85 neutralizer 70 within the chamber to neutralize any static charge on the droplets or residue particles.
  • the liquid is evaporated from the droplets 66 to produce residue particles 69 which are composed of organic and/or inorganic components.
  • the particles are drawn into a tube 72 controlled by a valve 74 which directs the particles by way of tube 76 or 78 to a particle size analyzer 80. A portion of the stream can be directed through tube 78 where it is exposed to heater 82. A comparison of the diameter of the particles which have passed through heater 82 with the diameter of those which have passed through tube 76 gives a determination of whether or not the residue particle is organic in nature.
  • FIG. 2 One type of particle size analyzer, a light scattering particle spectrometer, is shown schematically in FIG. 2. As shown, a particle 100 to be measured is made to pass through an incident light beam 102 causing the light to scatter as shown at 103. The light scattered is picked up by a collection optics system 104 which directs the light to a photomultiplier tube or light sensitive diode 106. The signal from the photomultiplier tube or light sensitive diode 106 is directed to an amplifier 108 and then to a read-out device 110.
  • a photomultiplier tube or light sensitive diode 106 The signal from the photomultiplier tube or light sensitive diode 106 is directed to an amplifier 108 and then to a read-out device 110.
  • the device which is preferred for measurements of residue particle diameters in the range of 0.1 um to 12 um is a laser light scattering particle spectrometer available from Particle Measuring Systems, Inc. Model LAS-X or LAS-250X. A schematic of this device is shown in FIG. 1.
  • a sample droplet generator substantially as shown in FIG. 3 monodisperses a liquid to be measured for impurities into uniform droplets in air, each droplet having a diameter D, which forms after evaporation, a residue particle sample having a diameter d.
  • This output of the droplet generator constitutes the particle source 10 shown in FIG. 1.
  • the residue particle sample stream issuing from particle source 10 is drawn through hypodermic tubing 18 having a 500 um diameter.
  • sheath air controlled by a flow meter 12 flows through filter 14 and is aerodynamically focused at nozzle 16 where the residue particle sample stream joins the flow of filtered sheath air.
  • the combined flow of filtered sheath air and the residue particle sample stream intersects a laser beam at point 20 before being drawn by pump 22 to filter 24.
  • Filter 24 collects the residue particles while permitting the passage of air which is directed to flow meter 26 and out of the system. Needle valves 25 and 27 control the amounts of air passing in and out of the system.
  • the laser 28 is a hybrid He-Ne 632.8 nm tube with an aluminum envelope especially designed for the laser.
  • the active laser cavity 30 is contained within a housing 32.
  • the laser 28 is used in conjunction with two front surface mirrors 34 and 36.
  • the first collecting surface mirror is a parabolic mirror 34 through which the particles to be analyzed pass through its focus during the sampling process.
  • the parabolic mirror 34 has been gold-plated to provide 90% reflectivity at 632.8 nm.
  • the second surface mirror 36 is at a 45° angle and is dielectrically coated to provide greater than 99% reflectivity at 632.8 nm.
  • An aspherical refracting element 38 which is also dielectrically coated is housed in a single aluminum block 40.
  • the laser cavity 30 is sealed by means of O-rings 42, 44 and 46. Also, at the point diametrically opposite from the laser 28 is an external mirror 48. A sealed mirror 50 is rotated between the laser and a reference photodetector module 52. A scattering photodetector module 54 completes the optical system.
  • the optical system described above supplies an energy density in excess of 500 W cm 2 with a beam width of 400 um-600 um.
  • the combined imaging system has an effective magnification of 4 ⁇ .
  • the system collects light from 35%-120% providing a 2.2 pi steradian solid angle.
  • the particle sampling takes place with the aerodynamically focused jet comprised of the particle sample stream from the particle source 10 surrounded by a filtered sheath air flow.
  • the particle sample stream is positioned at the focus of the parabolic mirror 34 at point 20 of FIG. 1.
  • Light collected from the laser is columnated by the parabolic mirror 34 and after reflecting off the 45° flat mirror 36, it is refocused by the aspheric lens 38.
  • the collected light is converted by the photodetector module 54 into a signal photocurrent.
  • An alternative device for measuring the diameter of residue particles which is especially suited for residue particles having a diameter d greater than about 0.5 um is an APS 33 aerodynamic particle sizer manufactured by TSI, Incorporated and which is shown schematically in FIG. 5.
  • the principle of the aerodynamic particle sizer is based on the fact that if one can measure the speed of an accelerating particle in a known flow field, one can measure its true aerodynamic size.
  • particles are drawn through a particle accelerating nozzle 120 to produce a precisely controlled accelerating high-speed jet of air.
  • the velocity of the particle is measured by a laser velocimeter. During the entire measurement period, the velocity at any point in the flow field remains constant within the jet, depending upon the aerodynamic size characteristics of the particle. Small particles will accelerate more rapidly than larger particles.
  • the particle speed is actually measured at the exit 122 of the particle accelerating nozzle 120.
  • the laser velocimeter system consists of a laser light source (not shown), a beam expander and splitter (not shown), focusing optics 124, receiving optics 126, and a photomultiplier light detection system 128.
  • an expanded laser beam is split to form two expanded and split laser light beams 130 which are then focused into two parallel planes immediately below the accelerating flow nozzle. Each particle passing through these two parallel planes produces two pulses of scattered light which are collected and focused onto the photomultiplier light detection system to produce two electrical pulses.
  • the time interval between the two pulses is measured by pulse time interval detector 132 and indicates the velocity of the particle and thus its aerodynamic size.
  • an electrostatic classifier in conjunction with a particle detector, for example a condensation nuclei counter.
  • An electrostatic classifier of the type described is manufactured by TSI, Inc.
  • the principle of the electrostatic classifier is illustrated schematically in FIG. 4.
  • the residue particle stream produced by a droplet generator is passed through a Kr-85 bipolar charger to establish a bipolar equilibrium charge level on the particles. Within the diameter size range of about 0.005 um to 0.3 um, most particles obtain a single positive or negative electrical charge unit.
  • the positively and negatively charged particles are then passed into a device substantially as shown in FIG. 4 which is a differential electrical mobility analyzer. This device removes all particles except those within a narrow mobility range, which range depends upon the voltage.
  • the particles enter the device at inlet 70 where they are carried along by means of a stream of air entering at inlet 74 through the device within a grounded chamber 72, and are placed into contact with a variable high voltage supply source 76. Within the chamber 72 all particles are removed except those within a narrow mobility range depending upon the voltage. As the voltage on the mobility analyzer is adjusted over its operational range, the residue particle exhaust stream of unknown diameter d exits chamber 72 through outlet 78 where it is directed to a condensation nuclei counter 81. When the condensation nuclei counter 81 detects particles, the diameter of the particles can be precisely determined from the knowledge of the mobility analyzer voltage, the constant flow rate, and the system geometry, since all the particles have a single charge.
  • condensation nuclei counter which can be used is Model 3020 manufactured by TSI, Inc.
  • butanol is made to condense on submicrometer particles which are passed over the surface of a butanol pool at a temperature of about 33° C.
  • the vapor condenses onto the particles causing them to grow to about 10 um droplets.
  • the particles with the condensed butanol vapor are then passed through a beam of a high intensity and reliable 10,000-hour halogen lamp.
  • the resulting forward light scattering is picked up by a photodetector which produces a photodiode output which has a high signal to noise ratio.
  • the analog output is linearly proportional to the concentration over the entire concentration range.
  • the process of the invention provides a means for the rapid measurement of sub-ppm concentrations of impurities in liquids.
  • the method allows the determination of both organic and inorganic impurities.
  • liquids to be measured for impurities should have a relatively low viscosity under ambient conditions which permits the generation of droplets. Also, they should be capable of being contained in an appropriate vessel with which such liquids would be nonreactive in order to avoid the introduction of additional impurities not present in the original liquid. Finally, the liquids should be capable of evaporation.
  • the liquid In order to measure the impurities in the liquid, it must first be dispersed into uniform droplets of a precisely known diameter D in a gas stream. While the drawings illustrate one type of droplet generator, any type of droplet generator can be employed which ultimately produces uniform droplets of a precisely known diameter D.
  • the liquid can be directly monodispersed using a monodisperse aerosol generator of the type described in FIG. 3.
  • a preferred device is Model 3450 available from TSI, Inc.
  • droplet diameter size can be within the range of 1 um to about 200 um, with preferably a droplet size range of about 20 um to about 50 um. The last range gives excellent results for impurity measurements at the ppm level.
  • the materials which are contacted by the liquid must be considered in order to achieve the most accurate results.
  • stainless steel is commonly used for the vibrator head and orifice plate in the vibrating orifice generator.
  • Teflon is the material used for tubing, gaskets, a filter, and a 13 mm filter that protects the micro-orifice.
  • polypropylene is the material commonly used in the filter holder. The syringe materials must also be considered. The exact choice of materials will depend on the type of liquid which is being used.
  • the polypropylene filter housing does not appear to react with most organic solvents or water.
  • the syringe includes not only the material of which it is made, but also a plunger. Satisfactory results have been obtained with a syringe of borosilicate glass with a Teflon plunger for the case of isopropanol. For water measurements, a polypropylene syringe with a neoprene plunger has given satisfactory results. It should be remembered though, that certain types of materials will react with the liquid to be measured, and each instance should be reviewed for the appropriate choice of materials.
  • the gas stream to be used for the generation of the droplets is ultrafiltered air.
  • any ultrafiltered gas such as nitrogen or other inert gas can be used as long as the gas is non-reactive with the liquid to be measured or with the impurities present.
  • the droplets are introduced into a turbulent gas flow to encourage the rapid evaporation of the liquid from the impurities to leave a residue particle having a diameter d.
  • the droplet generator can be equipped with a short heating section near the outlet in order to heat the gas particle stream.
  • the particles can be passed through this section to permit an estimate of whether the residue is of organic or inorganic origin. If the impurity consists of an organic residue, a diameter change will be observable after heating.
  • the difference between the diameter of the particle after passage through the heating section when compared with the diameter of a particle which has not been exposed to the heating section, permits the determination of the organic portion of the impurity by the difference in diameter.
  • the volume, V, of each droplet can be calculated from the operating parameters using the formula:
  • Q is the volume flowrate of liquid in the jet
  • F is the excitation frequency of the periodic disturbance.
  • the volume flow rate of the liquid Q needs to be redetermined in each case for each individual syringe.
  • the diameter D of the droplet is calculated by solving for D in the formula for the volume of a sphere:
  • the liquid volume flow rate can be measured by weighing the amount of liquid dispensed by the syringe pump over a given period of time. For example, 10 cm 3 can be injected into a small flask sealed with a septum to minimize evaporation. Error analysis has shown only negligible errors for time measurements, weighing and evaporation losses. It was found during a test duration of 64 minutes that evaporation from the open flask amounted to only 0.06 g. Only the last drop which amounted to about 0.05 cm 3 or about 0.5% for a liquid feed rate of 0.153 cm 3 /min. provided the main uncertainty. This resulted in a total uncertainty of less than ⁇ 1% in Q.
  • the diameter d of the residue particles is then determined.
  • the diameter of the residue particle determines the best choice of the device to be used.
  • FIG. 1 of the drawings An example of a preferred device is illustrated in FIG. 1 of the drawings with a schematic of a general type of this device shown in FIG. 2.
  • the device which is preferred is a light scattering particle spectrometer available from Particle Measuring Systems, Inc. Model LAS-X or LAS-250X.
  • the laser light scattering spectrometer measures an "optically equivalent sphere" diameter for particles which depend on shape and refractive index of particles. Particles such as NaCl crystals which are not perfectly round but are otherwise sphere-like and in the size range less than 1 um do not generally result in a source of systematic errors. The size differential results in a slight broadening of the pulse distribution which would not be noticeably within the laser light scattering spectrometer resolution.
  • Saline water droplets evaporate to form a dry solid particle whose volume size is constant and independent of humidity when the relative humidity is less than about 40%-50%.
  • the particles will begin to grow by absorbing water (deliquescence) at higher relative humidities.
  • the solid crystals of NaCl are cubes with rounded corners.
  • organic impurities and organic solvents can display a viscous oily nature.
  • the residue droplets thus formed are spherical in shape with a vapor pressure significantly below that of the solvent.
  • the resulting residue droplet is stable enough for analysis by various on-line size analysis techniques. When subjected to heat above ambient temperature, these droplets will evaporate to provide a means of determining whether the impurity is organic or inorganic in nature.
  • the combination of the vibrating orifice generator together with the laser light scattering spectrometer is preferred for measuring impurities in most liquids.
  • One reason is because the resolution and linearity of the light scattering spectrometer is best in a size range of less than 0.7 um.
  • an impurity concentration of 0.1 ppm-v to 125 ppm-v can be detected.
  • an aerodynamic particle sizer such as an APS 22 available from TSI, Incorporated, can be used.
  • an electrostatic classifier as shown in FIG. 4 can be used for size classification in conjunction with a particle detector such as a condensation nuclei counter.
  • a particle detector such as a condensation nuclei counter.
  • a preferred electrostatic classifier is available from TSI, Inc. and a preferred particle detecter is a condensation nuclei counter, Model 3020 manufactured by TSI, Inc..
  • Water and isopropyl alcohol were measured separately for impurity levels within the range of about 0.2 ppm to about 100 ppm taking measurements at 3 to 4 concentration levels for each liquid.
  • the water used was commercially available bottled DI water having an initial residue level of 0.16 ppmv as given by the invention method described below. As measured by the "residue after evaporation" method the residue level was 0.41 ppmw. Sodium chloride was dissolved in the water to provide impurity levels of 2 ppmw and above.
  • the isopropyl alcohol used was HPLC grade labeled at less than 2 ppm by the "residue after evaporation" method. Prior to heating of the residue, the measured impurity content was 0.8 ppmv and 0.6 ppmw respectively. After heating, all the residue evaporated. Impurity levels greater than 2 ppm were prepared by mixing the isopropyl alcohol with leachate from neoprene gasket material to provide impurity levels of between about 5 ppm and 100 ppm.
  • the devices used in measuring the impurities included a vibrating orifice generator substantially as shown in FIG. 3 and a laser light scattering spectrometer substantially as shown in FIG. 1.
  • the vibrating orifice generator used was Model 3450 of TSI, Incorporated.
  • a 20 um orifice was used and the liquid feed rate Q ranged from 0.153 cm 3 /min to 0.077 cm 3 /min.
  • the orifice was vibrated at a frequency in the range of 40 kHz-150 kHz.
  • the droplets were introduced into a turbulent flow of ultrafiltered air.
  • a droplet diameter size of 44 um was used for measurements for isopropyl alcohol and a droplet diameter size of 42 um and 23 um for the water measurements.
  • the residue particle diameter was measured using a laser light scattering spectrometer LAS-250X available from Particle Measuring Systems, Incorporated.
  • the syringes used included a borosilicate syringe with a Teflon plunger for isopropyl alcohol measurements, and a disposable polypropylene syringe with a neoprene plunger for water measurements. Water or isopropyl alcohol was used to fill the syringe followed by dispensing and atomizing small amounts of the liquid for a droplet size measurement at intervals of 20 minutes or one hour.
  • the "residue after evaporation" procedure followed was substantially as outlined by ASTM (American Society for Testing Materials) and SEMI (Semiconductor Materials Institute). Basically, each sample was evaporated at a temperature sufficient to maintain low evaporation rates. When water was measured for impurities, the dish was inerted with a coating that had been tested for constant weight over the range of operating temperatures. Evaporation was carried out under Class 100 clean room conditions. The volume of the fluid tested ranged from about 30 cm 3 to about 1000 cm 3 , the exact volume depending upon the levels of impurities present. A microbalance or semimicrobalance was used to determine weights, which choice was governed by the tare weight of the dish.
  • Tables I and II show that very high resolution and accuracy can be obtained by the invention method at very low impurity levels.
  • the residue or bulk evaporation technique has a detection limit of about 0.1 ppmw.
  • Table II shows that at higher concentrations of impurities there is good agreement between the results except in the case where the residue particle diameter size was 1.05 ⁇ 0.1 um and the droplet diameter size was 42 um. At the same impurity concentration, using a droplet diameter size of 23 um instead of 42 um, good agreement between the two methods was obtained, as shown in the last example of Table II.
  • Table I shows an uncertainty of ⁇ 30 for the measurement of isopropyl alcohol containing 110 ppmv concentration of impurities. This is due to the fact that the droplet diameter size of 44 um produces a residue particle which is too large to provide accurate measurement with the laser light scattering spectrometer. However, this can be overcome by using a smaller droplet diameter size initially. This would then provide a particle size which is within the scope of the laser light scattering spectrometer.
  • Tests were conducted, each of which had a duration of one day, in order to determine the contribution of possible impurities by the syringe material.
  • the results of the tests showed that for the isopropyl alcohol, the borosilicate glass syringe with a Teflon plunger showed no detectable fluctuation or drift of the results over time.
  • the method described herein provides for the rapid measurement of impurities in liquids especially at very low concentrations.
  • dispersing a droplet of the liquid to be measured, determining its diameter D, evaporating the droplet to leave a residue particle having a diameter d which is measured enables the determination of the concentration by volume C v in the original liquid according to the equation:
  • the method is rapid, each test being capable of completion in less than 5 minutes.
  • the method is reliably accurate as demonstrated by the results presented in Tables I and II, and inexpensive with regard to the relatively small amounts of the liquid which are required.

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Priority Applications (4)

Application Number Priority Date Filing Date Title
US06/801,305 US4794086A (en) 1985-11-25 1985-11-25 Method for measurement of impurities in liquids
JP62500195A JPH06105249B2 (ja) 1985-11-25 1986-11-21 液中の不純物測定方法及び装置
EP87900412A EP0247180A1 (fr) 1985-11-25 1986-11-21 Procede de mesure de concentrations d'impuretes dans des liquides
PCT/US1986/002530 WO1987003371A1 (fr) 1985-11-25 1986-11-21 Procede de mesure de concentrations d'impuretes dans des liquides

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JPS63501448A (ja) 1988-06-02

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